Polymerization of chloroethylene compounds in aqueous emulsion in the presence of amino-alcohols



Patented a. 18', 1949 POLYMEBIZATION or cnnonoirrr12mm:

COMPOUNDS m AQUEOUS EMULSION IN THE ransancn or arnnoar.conor.s

I Vernon L. Folt, Akron, Ohio, assignor to The B, F. I

Goodrich Company, New York, N.'Y'., a corporation of New York ,tainingfa single CHr=C group, 'that is, monomeric mono-vinylidene compoundsfleither alone or in admixture with one. another or with other unsaturated materials. The; invention more specifically relates to the polymerization in aque- Application June 12, 1941, serialize-154.260.

1M (01. ace-92s) in small amounts, thereby impairing the tra ous emulsion of monomeric materials comprised II predominantly of chlorethylenes such as vinyl chloride and vinylidene chloride.

It is well known that resinous linear polymers can be prepared by polymerization of monovinylidene compounds in aqueous emulsion, and obtained either as stable dispersions or latices or in the form of fine granular material. When vinyl chloride or vinylidene chloride is polymerized, it has been found desirable to maintainthe pH of the emulsion at or slightly above the neutral point in order to obtain stable dispersions of the resinous product and to achieve high yields. It has been observed, however, that the pH of a vinyl chloride emulsion, which is originally about'-8.0 to 8.5, drops steadily during polymerization until at: the end of the reaction the pH ranges from 3.0-3.5. Frequently, such an undesirable drop in pH makes it necessary to carry out the reaction at lower temperatures "and for an excessively long time in order to obtain satisfactory yieldsr It is also 'known that certain substances, may

be incorporated in a vinyl chloride polymerization mixture to actas buffers to maintain the I pH at or above the-neutral point. For example, lead acetate, salts of strong bases and weak acids such as sodium bicarbonate, sodium acetate and the like, have been utilized as buffers in vinyl chloride polymerizations. However, the use of v such substances is subject to many disadvantages,

for example, they introduce metallic ions into the polymerization mixture, which ions often adversely affect the chemical and physical stability and electrical properties of the resultantpolymer. Still another disadvantage of many of these compounds is that they break down under polymerization conditions or react with hydrogen chloride liberated during polymerization to evolve acidic substances, (carbon dioxide in the case of sodium bicarbonate or acetic acid in the case of lead acetate and sodium acetate) all of I which tend to change the pH in an unpredictable fashion. Moreover, some of the buffering substances known to the art fail to maintain the pH at the neutral point unless used in such large amounts that they become diflicult to remove from the polymer and are retained in the polymer parency and clarity of the finished resin.

For these and other reasons, it is desirable that the pH of the polymerization mixtures be maintained at or above the neutral point, and that, generally speaking, the substance used as a buffer be capable of maintaining the pH of the reaction mixture at the desired point when present in small amounts and be free or metallic ions, in order to avoid formation of an unstable dispersion and to prevent an adverse eflect on the electrical properties and clarity of the polymer. Accordingly, it is the principal object of this invention to provide buffering substances for use in emulsion polymerization of vinyl chloride and other monomers which will possess these properties and be freed the above-mentioned defects. Another object is to provide materials which act both as buffers and, emulsifiers. Other objects will be apparent from the following description.

' this invention which comprises polymerizing a monomeric mono-vinylidene compound in an aqueous emulsion containing an aliphatic aminosubstituted alcohol such'as 2-amino-2-methyll-propanol. The amino-substituted alcohols are sufllciently basic in character and so readily take up hydrochloric acld'that small amounts are capable of maintaining the pH of a vinyl chloride polymerization mixture in the desired range of 7.0 to 8.5 without the liberation of undesirable reaction products. Furthermore, rapid polymerizations are possible b the use of the-aliphatic amino-substituted alcohols, and yields of 90 to substantially 100% are generally obtained within about 16 to 24 hours.

Contrary to usual practice, which is to polymerize the monomeric material in an evacuated system or in an inert atmosphere, I have found that when using such amino-substituted alcohols it is preferable to carry out the polymerization of mono-vinylidene compounds in the presence of gaseous oxygen. For example, when the polymerlzatlon of a vinyl chloride emulsion containing an amino-substituted alcohol is attempted in an evacuated polymerization vessel, or in the presence of an inert atmosphere such as nitrogen, I have found that polymerization at temperatures of to C. and times of 40 to 60 hours or more are required, but when the ingredients of the emulsion are charged'to the reaction vessel and the vessel sealed in a manner as to entrap considerable air, polymerization begins immediately and yields of to substantially are obtained in about 16 to 24 hours. This result is quite surprising since both gaseous oxygen and compounds containing amino groups generally inhibit polymerization.

t has also been found that the aliphatic amino-substituted alcohols employed in the method of this invention not only act to maintain the pH of the reaction mixture at or slightly above the neutral point, but also serve to emulsii'y the monomeric material during polymerization and to stabilize the latex-like dispersion obtained. Accordingly, smaller than normal amounts of ordinary emulsifying agents may be employed, when an aliphatic amino-substituted alcohol is present. Ordinary emulsifying agents may even be omitted entirely and the aliphatic amino-substituted alcohol used in the dual capacity of emulsifier and bufler, for example. vinyl chloride may be polymerized in aqueous emulsion in the presence of an amino-substituted alcohol and in the absence of any other emulsifying agent to yield an excellent polymer.

The method of this invention is applicable to the emulsion polymerization of any mono-vinylidene compound, i. e,, any monomeric material which contains a single oleflnic bond linking a methylene group to a carbon atom in the structure CH2=C which undergoes addition polymerization in aqueous emulsion to form a linear polymer. Illustrative examples of such 'monomers are vinyl halides such as vinyl chloride. vinyl bromide or vinyl fluoride: vinyl esters such as vinyl acetate. vinyl chloroacetate, vinyl propionate, vinyl butyrate, and others: vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl 2-chloroethyl ether, and others; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone. vinyl isopropenyl ketone, and others; ethylene; isobutylene; styrene, and p-chlorostyrene; esters of alpha-methylene aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, 2-chloropropyl acrylate, 2,2'-dichloro-isopropyl acrylate. phenyl acrylate, cyclohexyl acrylate, methyl alpha chloro acrylate, methyl methacrylate. ethyl methacrylate, methyl ethacrylate, and others; vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride; N-vinyl compounds such as N-vinyl pyridine, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl succinimide, and others; and other similar polymerizable materials. All these materials are monovinylidene compounds. it being understood that mono-vinyl compounds contain the vinylidene struct re CH2=C and are hence a sub-genus of mono-vinylidene compounds. The method of this invention is also applicable to the polymerization of mixtures of two or more of these monomeric materials and to the polymerization of mixtures of these compounds with other unsaturated monomers including other compounds containing a single oleflnic bond such as the alkyl esters of maleic and fumaric acids, and even monomers containing more than one double bond such as butadiene-1,3, chloroprene, diallyl maleate. etc.

The invention is most applicable to the polymerization of these monomeric materials which comprise predominantly a chloroethylene containing from one to two chlorine atoms on one only of the carbon atoms. and having only hydroen atoms attached to the remaining valences of the ethylenic carbon atoms. Included in such materials are. for example, vinyl idene chloride, mixtures of these monomers with each other and with lesser proportions of other copolymerizable mono-vinylidene compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, esters of alpha-methylene aliphatic monocarboxylic acids, particularly alkyl acrylates and methacrylates such as methyl acrylate, ethyl I acrylate, methyl methacrylate, ethylmethacryformula NH2R(OH) wherein R is an allchloride, vinyl-.

r are not intended 1 thereof.

phatic hydrocarbon radical containing from 2 to 6 carbon atoms, and n is an integer from 1 to 3. Examples of compounds which may be used in the present invention are:

Z-amino-ethanol 2-amino-2-methyl-1-propanol 2-amino-2-methyl-1,3-propanediol 2-amino-2-ethyl-1,3-propanediol 3-amino-2-methyl-l-propanol 2-amino-1-butanol 3-amino-2,2-dimethyl-1-propanol 2-amino-2,3-dimethyl-1-propanol 2,2-diethyl-2-amino ethanol 2,2-dimethyl-2-amino ethanol 3-amino-1,2-butanediol 4-amino-1,2-butanediol 2-amino-1,3-butanediol 4-amino-L3-butanedio1 4,4-dimethyl-1,3-butanediol 2-amino-1,4-butanediol 3-amino-1,4-butanediol l-amino-2,3-butanediol 4 Tris-(hydroxy methyl) amino methane The amount of aliphatic amino-substituted alcohol which is used may vary from as little as 0.1% to as much as 5% by weight based on the monomeric material. maintain a stable dispersion without appreciable coalescence and coagulation will, of course, depend on the type and amount of other emulsifying or dispersing agents used, if any, and the monomer being polymerized. If the amino-substituted alcohol is used alone in the dual capacity of emulsifier and buffer, larger amounts are used than when another emulsifying agent is present. For example, when 0.6 to 1.0% of a synthetic saponaceous emulsifying agent (such as, for example, sodium isobutyl naphthalene sulionate) is used as the primary emulsifying agent, about 0.30 to 1.5% of the amino-substituted alcohol is sufllcient to act as a buil'er. When used alone, it has been found that 0.8 to 1.5% or more of the amino-substituted alcohol is desirable.

The following specific examples are given as illustrations of the nature of this invention, but as a limitation upon the scope EXAMPLES 1 To 3 To illustrate the action of the aliphatic aminosubstituted alcohols in the dual capacity of emulsifying agent and buffer, emulsions containing the following materials were prepared and then agitated at 50 C. to bring about polymerization of the monomeric materials present.

Material Amount Vinyl. chloride parts Dlethyl chloromaleate do 10 2-amino-2-methyl-l-propanol Variable 0,0-dichlorobenzoyl peroxide part 0.3 Atmosphere Air The amount necessary to I The amounts of 2-amino-2-methyl-l-propano1 used were respectively 0.25, 0.50 and 1.0 parts. In all cases the polymerization required only 16 to 24 hours to produce a 95 to 100% yield of a fine granular polymeric product which was possessed of excellent physical and electrical properties and could be plasticized to give a clear, transparent illm. The pH of the aqueous phase was found to range from 6.5 to 8.0. when no amino Material cmer accordingv to the lo o Recipe inantly of vinyl chloride or of vinyl chloride alone.

alcohol was used, however, the pH dropped to l M n r 1} below 3.0, and the polymerization requiredam'uch Monomer .2 longer time. Water Sodium isobutyl naphthalene jsul EXAMPLES 4 T 9 y 2-amino-z-methyl-1 propanol The results of the above examples indicate that 15 o o dichlombemyl peroxide a-amino-z-methyl-l-propanol operates very eiiectively to give desirable copolymers. The following examples were periormed'in order to evaluate a number 01' the amino-substituted alcohols and v to determine the optimum amou nts necessary to The followingtable maintain the pH. The following materials were results:

Example Monomers-rem by Weight mg legal Per 28 10 Diethyl Maleate (50); Vinyl Chloride (50)- 0.10 04.4 Per cent chlorlne theo 'irensparentPolymer. l1 Diethyl Fumarate (l0); Methyl Acryllte 3.90 0L0 Polymerinsolubleinmethyl hylhetone;

(00). a and nltrobenzene; soft, jspongy an *transparent spheres of -polymer,'-c

' andcolorlessmoldirggs. 3 t- I, I l2 Vinyl Chloride (40); Diallyl Chioromaleate 0.54 94.3 Polylmer is-ln the form of spherical halls! (00). I w ich are hard and glassyproduces V mbbgrymqmmgs'f, l3 Vinyl Acetate (05); DimethylMaleate (5). 0.54- v 94.3 Polymerelear andh d. I 14 Dlethyl Maleate(),Vinyl Acetate (00). 0.00 7 00.3 Transparentsphere i'polym subjected to polymerization conditions in small In addition, resinous c0polyjr n rs J H A glass tubes: in yields of 90% or morebypolymerizin Mat rial: am an 1 mbl e e amib vli yl hloride arts 103 an m u i t s cehq il fi l 9' h water 250 methods shown in the pr cedin examp Sodium 'isobutyl naphthalene Vinylldenechloride -nbutyflmalea H.

sulfonate do- .625 Vinylidene chloride-viny1chlride thylmale; Amino-substituted alcohol a Variable 'ate 0,0'-dlchiorobenzoyl peroxide -..part 0.3 Methyl crotonateethylacrylate, Temperature -..C.' 50 Dialkyl chloromaleate-vihyl chloride Atmosphere Air Styrene-allylhydracmiale N-butyl maleate---acrylomtrile v I P .Vinyl chloride-winylacetate; 3g}: .Amlnosubstituted alcohol Yield Vinyl chloride-vinyl isqpropgl ei:,pgr r 13;"; g; Vinylidene chloride-vinyl isomQDYLothe y y Vinyl chloride-Z-yinyl fur-ape am Vinyl chloride-diethyl onoehlor maleat 4 2-?lsg2lg-2-methyl-l-propanol, 0s 0. 40 3.51 h l r g y dg e o ride a grams. my 0 0! e-acryo I, l 8 s ZEK:;;% D opme- 0.00 8.91 vi ylidene chloride-acrylonitrile v 0 ith; 0.00 0.03 0.83 Any of the usual dispersing agents such as th 5 %fi 8f; 3 g g sodium and potassium salts of fatty acids and the diol 0.0021. synthetic saponaceous materials may be employed 9 @gggggrggggggw in coniunction with the aliphatic amino-substituted alcohols. The synthetic saponaceous ma- From the foregoing, it is seen that, generally, terials such as the hymolal sulfates and alkaryl 0.6% to 0.93% or more of the amino-substituted mummies are Preferred the Practice this alcohol is necessary to maintain the when invention, for example, sodium lauryl sulfate, using another l if in agent with the ammo sodium isopropyl naphthalene sulfonate, sodium substituted alcohol. It is also seen that for some imbuty] naphthalene sulfonate' and mate of the ammmsubs'tiwted alcohols tested, as much rials as the dialkyl succinamates, the sodium salt as 1.2 to 1.5% of alcohol is necessary to maintain or iN'octadecyl'n' Lz'dica'rboxyethyl sulfosuc' the It is also to be noted. that m most cases cinamate, etc. Mixtures-of two or more dispersthe yields ranged from to substantially mg agents may 8180 be f r example, a mix- EXAWS 10 TO M 70 ture of equal proportions of the latter compound in the above list and sodium lauryl benzene sulhe foregoing p c c examples describe the tonate gives excellent results when combined with Process f hi invention ppli d to the polymerthe aliphatic amino-substituted alcohols oi this ization of monomeric mixtures consisting Dr dominvention.

"Any of the usual peroxygen-type catalysts, in-

assaavo stead of the one described in the specific example, may be employed in the process of this invention: for example, benzoyl peroxide, caprylyi peroxide, hydrogen peroxide, ammonium persuliate, sodium perborate, the percarbonates, the persuliates, or the like or mixtures of two or more or such materials may be used. Other modifying or catalyzing substances may be used as is well understood by the art.

The polymerization according to the method this invention may be carried out at temperatures from to 90 C. but according to the preferred practice of the art, polymerization at temperatures of 40 to 60 C. will result in superior polymerizates and moreover will accomplish substantially complete reaction in a reasonable time.

'The present application is a continuation-inpart oi my copending application. Serial No.

519,913, nled January 27, 1944, andentitled Polymerization of vinyl chloride and vinyiidene chloride with dialkyl esters of chloromaleic acids, now abandoned.

While there has been disclosed with considerable detail certain preferred manners oi performing this invention, it is not intended or desired to be solely limited thereto, for as hitherto stated the procedure may be modified, the precise proportions of the materials utilized maybe varied, and other materials having equivalent properties may be employed if desired without departing from the spirit and scope oi the invention as delined in the appended claims.

I claim:

1. The method which comprises polymerizing a monomeric material comprising predominantly a chloroethylene having from one to two chlorine atom on one only of the carbon atoms, and hav ing only hydrogen atoms attached to the remaining valences of the ethylenic carbon atoms, in aqueous emulslonin the presence of an aliphatic amino-substituted alcohol oi the structure NHa-R-(OHM wherein R is an aliphatic hydrocarbon radical containingfrom 2 to 6 carbon atoms and n is an integer from 1 to 3.

2. The method which comprises dispersing a monomeric material comprising predominantly a chloroethylene having from one to two chlorine atoms on one only of the carbon atoms, and having only hydrogen attached to the remaining valences oi the ethylenic carbon atoms in an aqueous media comprising a peroxygen type catalyzing substance and an aliphatic amino-substituted alcohol of the structure NHa-R-(OH); wherein R is an aliphatic hydrocarbon radical containing from 2 to 6 carbon atoms and n is an integer from 1 to 3 and heating the aqueous emulslon containing the monomeric material at a temperature of from 30 to C. to accomplish polymerization of said monomeric material.

3. The method which comprises polymerizing a monomeric material comprising predominantly vinyl chloride in aqueous emulsion in the presence of an aliphatic amino-substituted alcohol 01' the structure Nils-.R-(OH); wherein R. is an aliphatic hydrocarbon radical containing from 2to6carbon atoms andnis an integer from 4. The method of polymerization which comprises polymerizing vinyl chloride in aqueom emulsion in the presence of an aliphatic aminosubstituted alcohol of the structure wherein R. is an aliphatic hydrocarbon radical containing from 2 to 6 carbon atoms and n is an integer from 1 to 3.

5. The method which comprises dispersing a monomeric material comprising predominantly vinyl chloride in an aqueous media comprising a peroxygen type catalyzing substance, an aliphatic amino-substituted alcohol oi the structure wherein R is an aliphatic hydrocarbon radical containing from 2 to 6 carbon atoms and n is an integer from 1 to 3 and gaseous oxygen, and heating the aqueous emulsion oi monomeric material at a temperature of from 30 to 90 C. to initiate polymerization.

6. The method which comprises polymerizing a monomeric material comprising predominantly a chloroethylene having from one to two chlorine atoms on one only of the carbon atoms, and having only hydrogen atoms attached to the remainingvalences oi the ethylenic carbon atoms, in aqueous emulsion in the presence of 2-amino-2- methyl-l-propanol.

'7. Themethod which comprises polymerizing a monomeric material comprising predominantly of vinyl chloride in aqueous dispersion in the presence of 2-amino-2-methyl-1-propanol.

- VERNON L. FOLT.

mcrruuuscris cr mp The following references are 01' record in the iile of this patent:

I UNITED STATES PATENTS Number Name Date 2,393,438 Weisberg Jan. 22, 194

Brubaker- June 17, 194'! Certificate of Correction Patent No. 2,485,270 October 18, 1949 VERNON L. roizr It is hereby certified that errors appear in the printed specification of the abov numbered patent requiring correction as follows:

Column 2, line 4, for the word "mixtures reed mixture; column 6, line 15; for 0,0-dichlorobenzoyl" read 0,0-d'ichlorobenzoyl;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 30th day of May, A. D. 1950.

THOMAS F. MURPHY,

Assistant of Putcnts. 

